EP0835293A1 - Compositions pour enduits contenant des polymeres acryliques a groupes carbamate pendants - Google Patents
Compositions pour enduits contenant des polymeres acryliques a groupes carbamate pendantsInfo
- Publication number
- EP0835293A1 EP0835293A1 EP96919448A EP96919448A EP0835293A1 EP 0835293 A1 EP0835293 A1 EP 0835293A1 EP 96919448 A EP96919448 A EP 96919448A EP 96919448 A EP96919448 A EP 96919448A EP 0835293 A1 EP0835293 A1 EP 0835293A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- polymer
- oligomer
- percent
- forming composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 44
- 239000008199 coating composition Substances 0.000 title abstract description 20
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 title description 20
- 239000000203 mixture Substances 0.000 claims abstract description 109
- 229920000728 polyester Polymers 0.000 claims abstract description 90
- 239000002253 acid Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 229920003180 amino resin Polymers 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 230000001464 adherent effect Effects 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 56
- 229920000642 polymer Polymers 0.000 claims description 50
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 46
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- -1 poly(ester urethanes Chemical class 0.000 claims description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 15
- 238000005227 gel permeation chromatography Methods 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 15
- 125000004185 ester group Chemical group 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 description 77
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 50
- CATSNJVOTSVZJV-UHFFFAOYSA-N Heptan-2-one Natural products CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 32
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 22
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 21
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 21
- 238000002156 mixing Methods 0.000 description 21
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 21
- 229920003270 Cymel® Polymers 0.000 description 20
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000010790 dilution Methods 0.000 description 14
- 239000012895 dilution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 13
- 238000007792 addition Methods 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 4
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 4
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- AYIRHANHVDOYDJ-UHFFFAOYSA-N 3-hydroxypropyl propanoate Chemical compound CCC(=O)OCCCO AYIRHANHVDOYDJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical group O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229940072282 cardura Drugs 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- RUZYUOTYCVRMRZ-UHFFFAOYSA-N doxazosin Chemical compound C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 RUZYUOTYCVRMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001982 poly(ester urethane) Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical class CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- ZAXXZBQODQDCOW-UHFFFAOYSA-N 1-methoxypropyl acetate Chemical compound CCC(OC)OC(C)=O ZAXXZBQODQDCOW-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- BSBQJOWZSCCENI-UHFFFAOYSA-N 3-hydroxypropyl carbamate Chemical compound NC(=O)OCCCO BSBQJOWZSCCENI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- KWXICGTUELOLSQ-UHFFFAOYSA-N 4-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- LHOKCCUPZYSAJG-UHFFFAOYSA-N 6-oxohexyl acetate Chemical compound CC(=O)OCCCCCC=O LHOKCCUPZYSAJG-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920003265 Resimene® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000013036 UV Light Stabilizer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N methanediimine Chemical compound N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005392 polarisation enhancment during attached nucleus testing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31794—Of cross-linked polyester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
Definitions
- the present invention relates to film-forming compositions containing acrylic polymers with pendant carbamate groups in combination with crosslinking agents for 10 such polymers, and to the use of such film-forming compositions as clear coats in color plus clear composite coatings.
- Coating compositions based on acrylic polymers and aminoplast crosslinking agents are particularly desirable as automotive top coats because they have excellent durability, hardness, gloss and appearance. However, such coating compositions, when used as clear coats in color plus clear
- Acid etching is a phenomenon associated with acidic rain water, which is common in many urban and industrial areas.
- acidic rain water also known as acid rain
- acid rain accumulates on a horizontal section of an automobile such as a
- acrylic polymers containing pendant or terminal carbamate groups can be cured with aminoplast crosslinking agents to give acid etch resistant clear coats.
- a problem associated with curable coating compositions based on acrylic polymers containing pendant carbamate groups and aminoplast curing agents is that the compositions do not have particularly good intercoat adhesion. This problem presents itself when the compositions are used as clear coats in composite color plus clear composite coatings, especially during repair procedures which involve applying the clear film-forming composition to a flawed area of a previously applied color plus clear composite coating. The clear coats can actually delaminate from underlying layers of film.
- adhesion problems associated with film-forming compositions based on acrylic polymers containing pendant carbamate groups and aminoplast curing agents can be alleviated by using fully alkylated aminoplast curing agents and by including in the coating composition certain amounts of a polymer or oligomer containing a plurality of repeating ester groups in the polymer or oligomer backbone.
- the polymer or oligomer is added in amounts sufficient to increase the intercoat adhesion, but not in amounts that will significantly adversely affect the humidity resistance of the coating.
- the present invention provides an adherent film- forming composition comprising:
- (c) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent; the percentages by weight of (a) and (b) being based on total resin solids weight of (a) plus (b) ; the percentage by weight of (c) being based on total weight of resin solids in the film-forming composition.
- the percentage by weight of (a) plus (b) is from 25 to 75 percent by weight and is based on the total weight of resin solids in the film-forming composition.
- the present invention provides a method of applying a composite color plus clear coating to a substrate in which the film-forming composition described above is the clear coat. Further, the present invention provides for coated articles prepared by the above described method.
- R is H or CH 3 - Z is a repeating unit derived from one or more polymerizable ethylenically unsaturated monomers; and I is present in amounts of 30 to 70 percent by weight, Z is present in amounts of 30 to 70 percent by weight, with the percentage of I plus Z being equal to 100 percent.
- Y represents a divalent linking group, preferably an aliphatic group of 1 to 8 carbon atoms; or a cycloaliphatic or aromatic linking group of 6 to 10 carbon atoms including substituted groups. Examples of Y include
- -Y- is represented by -COO-Y'- where Y' is a divalent linking group.
- Y' can be a divalent aliphatic linking group, preferably of 1 to 8 carbon atoms, e.g., - (CH 2 ) - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, and the like; or a divalent cycloaliphatic linking group, preferably of up to 8 carbon atoms, e.g., cyclohexyl, and the like.
- the linking group Y' would include an -NHCOO-urethane linkage as a residue of the isocyanate group.
- the acrylic polymers are copolymers of one or more alkyl esters of acrylic acid or methacrylic acid, and, optionally, one or more other polymerizable ethylenically unsaturated monomers.
- Suitable alkyl esters of acrylic or methacrylic acid include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.
- Suitable other polymerizable ethylenically unsaturated monomers include vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride; vinyl esters such as vinyl acetate; and acid functional monomers such as acrylic and methacrylic acid.
- Hydroxyl functional monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate can be copolymerized with the acrylic monomers to impart hydroxyl functionality to the acrylic material preferably prepared in accordance with the theoretical hydroxyl values mentioned below.
- Pendant carbamate functional groups can be incorporated into the acrylic polymer by copolymerizing the acrylic monomers with a carbamate functional vinyl monomer, for example a carbamate functional alkyl ester of methacrylic acid.
- carbamate functional alkyl esters are prepared by reacting, for example, a hydroxyalkyl carbamate, such as the reaction product of ammonia and propylene carbonate, with methacrylic anhydride.
- carbamate functional vinyl monomers examples include the reaction product of hydroxyethyl methacrylate, isophorone diisocyanate, and hydroxypropyl carbamate; the reaction product of isocyanic acid (HNCO) with a hydroxyl functional acrylic or methacrylic monomer such as hydroxyethyl acrylate, and those described in U.S. Patent 3,479,328.
- Pendant carbamate groups can also be incorporated into the acrylic polymer by reacting a hydroxyl functional acrylic polymer with a low molecular weight alkyl carbamate such as methyl carbamate.
- hydroxyl functional acrylic polymers can be reacted with isocyanic acid yielding pendant carbamate groups. Note that the production of isocyanic acid is disclosed in U.S. Patent 4,364,913.
- hydroxyl functional acrylic polymers can be reacted with urea to give an acrylic polymer with pendant carbamate groups.
- the acrylic polymer can be prepared by solution polymerization techniques in the presence of suitable initiators such as organic peroxides or azo compounds, for example, benzoyl peroxide or N,N-azobis(isobutyronitrile) .
- suitable initiators such as organic peroxides or azo compounds, for example, benzoyl peroxide or N,N-azobis(isobutyronitrile) .
- the polymerization can be carried out in an organic solution in which the monomers are soluble by techniques conventional in the art.
- the acrylic polymer can be prepared by aqueous emulsion or dispersion polymerization techniques well known in the art.
- the acrylic polymer typically has a weight average molecular weight of from about 1000 to 30,000, preferably from about 2000 to 10,000 as determined by gel permeation chromatography using polystyrene as a standard, and an equivalent weight of less than 5000, preferably within the range of 140 to 2500, based on equivalents of reactive pendant carbamate groups.
- the equivalent weight is a calculated value based on the relative amounts of the various ingredients used in making the acrylic material and is based on the solids of the acrylic polymer.
- the film-forming composition contains a second resinous material comprised of repeating monomer units having a plurality of repeating ester groups in the backbone.
- This can be a polymeric or oligomeric material, and typically is an oligomeric polyester, a polymeric polyester and/or a polyurethane such as those prepared from polyester polyols and polyisocyanates.
- the polymers or oligomers having a plurality of ester groups in the backbone are prepared by a condensation or addition reaction in which the ester groups are repeating, i.e., 0
- a suitable polyester can be prepared by the esterification of a polycarboxylic acid or an anhydride thereof with a polyol and/or an epoxide.
- the polycarboxylic acids used to prepare the polyester consist primarily of monomeric polycarboxylic acids or anhydrides thereof having 2 to 18 carbon atoms per molecule.
- the acids that are useful are phthalic acid, hexahydrophthalic acid, adipic acid, sebacic acid, maleic acid, and other dicarboxylic acids of various types. Minor amounts of monobasic acids can be included in the reaction mixture, for example, benzoic acid, stearic acid, acetic acid, and oleic acid. Also, higher carboxylic acids can be used, for example, trimellitic acid and tricarballylic acid. Anhydrides of the acids referred to above, where they exist, can be used in place of the acid.
- lower alkyl esters of the acids can be used, for example, dimethyl glutarate and dimethyl terephthalate.
- Polyols that can be used to prepare the polyester include diols such as alkylene glycols. Specific examples include ethylene glycol, 1, 6-hexanediol, neopentyl glycol, and 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.
- glycols include hydrogenated Bisphenol A, cyclohexanediol, cyclohexanedimethanol, caprolactone-based diols such as the reaction product of e-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyether glycols such as poly(oxytetramethylene)glycol, and the like.
- the polyol component can comprise all diols, polyols of higher functionality can also be used. It is preferred that the polyol be a mixture of at least one diol; and at least one triol, or one polyol of higher functionality.
- polyols of higher functionality examples include trimethylol ethane, trimethylol propane, pentaerythritol, and the like. Triols are preferred.
- the mole ratio of polyols of higher functionality to diol is less than 3.3/1, preferably up to 1.4/1.
- a polyester is prepared from an esterdiol such as 2,2' -dimethyl-3-hydroxypropyl-2,2' - dimethyl-3-hydroxypropionate and a triol such as trimethylolpropane.
- the polyester can be nonfunctional or, preferably, it can contain functional groups that are reactive with the crosslinking agent described below.
- suitable functional groups include hydroxyl groups, carboxylic acid groups, or carbamate groups.
- Functional groups such as hydroxyl groups and carboxylic acid groups can be incorporated into the polyester by choosing appropriate ratios of polycarboxylic acids, anhydrides, polyols or epoxides for the esterification reaction, as is well known in the art.
- Nonfunctional polyesters can be prepared from functional polyesters such as hydroxyl functional polyesters by reacting them with a material such as isopropenyl acetate to consume the functional groups, rendering the resulting polyester essentially nonfunctional.
- the hydroxyl content will preferably be maintained in accordance with the theoretical hydroxyl values given below.
- hydroxyl- functional polyesters are used, they preferably are present in the film-forming composition at levels of 20 to 60, more preferably 20 to 40 percent by weight.
- the acrylic polymer is preferably present in amounts of 40 to 80, more preferably 60 to 80 percent by weight. The percentages are based on the total solids weight of the acrylic polymer and the polyester.
- the polyester has pendant and/or terminal carbamate groups of the structure:
- the carbamate groups can be incorporated into the polyester by first forming a hydroxyalkyl carbamate that can be reacted with the polyacids and polyols used in forming the polyester.
- a polyester oligomer can be prepared by reacting a polycarboxylic acid such as those mentioned above with a hydroxyalkyl carbamate.
- An example of a hydroxyalkyl carbamate is the reaction product of ammonia and propylene carbonate.
- the hydroxyalkyl carbamate is condensed with acid functionality on the polyester or polycarboxylic acid, yielding terminal carbamate functionality.
- Terminal carbamate functional groups can also be incorporated into the polyester by reacting isocyanic acid or a low molecular weight alkyl carbamate such as methyl carbamate with a hydroxy functional polyester.
- carbamate functionality can be incorporated into the polyester by reacting a hydroxy functional polyester with urea. If polyesters containing carbamate functional groups are used, they are preferably present in the film-forming composition at levels of 40 to 80 percent, more preferably 40 to 60 percent by weight. With carbamate functional polyesters, the acrylic polymer is preferably present in amounts of 20 to 60, more preferably 40 to 60 percent by weight. The percentages are based on the total solids weight of the acrylic polymer and the polyester.
- polyesters other polymers or oligomers having a plurality of repeating ester groups in the polymer or oligomer backbone such as polyurethanes can be used.
- Suitable polyurethanes can be formed by reacting a polyisocyanate with a polyester having hydroxyl functionality, and preferably containing pendant and/or terminal carbamate groups.
- polyurethanes can be prepared by reacting a polyisocyanate with a polyester polyol and a hydroxyalkyl carbamate or isocyanic acid as separate reactants.
- suitable polyisocyanates are aromatic and aliphatic polyisocyanates, with aliphatic materials being preferred because they impart better color and durability properties to cured composite films.
- suitable aromatic diisocyanates are 4,4' -diphenylme hane diisocyanate, 1,3- phenylene diisocyanate, 1,4-phenylene diisocyanate, and toluene diisocyanate.
- suitable aliphatic diisocyanates are straight chain aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate. Cycloaliphatic diisocyanates are preferred because they impart hardness to the product.
- Suitable cycloaliphatic diisocyanates include 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, ⁇ , ⁇ '-xylylene diisocyanate and 4,4' -methylene-bis- (cyclohexylisocyanate) .
- the amount of the polyurethane is the same as that for the polyesters mentioned above. Mixtures of polyesters and polyurethanes can be used.
- the polyesters and polyurethanes typically have weight average molecular weights of about 1000 to 30,000, preferably 1000 to 10,000 as determined by gel permeation chromatography using polystyrene as a standard.
- the equivalent weight of the polyesters and polyurethanes containing functional groups will be from about 140 to 2500, based on equivalents of functional groups.
- the equivalent weight is a calculated value based on the relative amounts of the various ingredients used in making the polyester or polyurethane, and is based on the solids of the material.
- the fully alkylated aminoplast crosslinking agent has a plurality of functional groups, for example, alkylated methylol groups, that are reactive with the pendant carbamate groups present in the acrylic polymer and with any functional groups associated with the polyester or polyurethane.
- Aminoplast crosslinking agents are obtained from the reaction of formaldehyde with an amine and/or an amide.
- Melamine, urea, or benzoguanamine condensates are preferred.
- aminoplast condensates prepared from other amines or amides can be used, for example, aldehyde condensates of glycouril, which are useful in formulating powder coatings.
- formaldehyde is used as the aldehyde; however, other aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde are also suitable.
- the preferred aminoplast crosslinking agent is a melamine-formaldehyde condensate that has been fully alkylated, that is, the melamine-formaldehyde condensate contains methylol groups that have been further etherified with an alcohol, preferably one that contains 1 to 6 carbon atoms.
- an alcohol preferably one that contains 1 to 6 carbon atoms.
- Any monohydric alcohol can be employed for this purpose, including methanol, ethanol, isobutanol, and cyclohexanol. Most preferably, a blend of methanol and n- butanol is used, resulting in a melamine-formaldehyde condensate that is, on average, 75 percent methylated and 25 percent butylated.
- the film-forming composition has a calculated hydroxyl value of less than 50, more preferably less than 25, and most preferably 0, based on the solid weight of the film-forming composition.
- the calculated hydroxyl value is calculated from the relative amounts of the various ingredients used in making the film-forming composition, rather than from an experimental titration measurement. Hydroxyl values greater than 50 are undesirable because they result in cured films with poor acid etch resistance.
- amounts greater than 80 percent by weight are undesirable because intercoat adhesion properties of cured films suffer; whereas amounts less than 20 percent by weight are undesirable because the humidity resistance of cured films suffers.
- amounts greater than 80 percent by weight are undesirable because the humidity resistance of cured films suffers; whereas amounts less than 20 percent by weight are undesirable because intercoat adhesion properties of cured films suffer.
- amounts greater than 50 percent by weight are undesirable because of poor acid etch resistance in the cured film; whereas amounts less than 25 percent by weight are undesirable because of poor cured film properties.
- the film-forming composition improves the intercoat adhesion. This is evident when the film-forming composition is used as the clear coat in a color plus clear composite coating. The improvement in intercoat adhesion is particularly evident during clear-on-clear repair procedures, in which an area of color plus clear composite coating which is flawed is overcoated with another layer of clear (without sanding) .
- the topmost layer of clear coat i.e., the repair coat
- the repair coat becomes part of an adherent composite coating.
- a diluent can be present in the film- forming composition that serves to reduce the viscosity of the coating composition.
- the diluent typically comprises an organic solvent.
- suitable solvents include alcohols such as ethanol, isopropanol, n-butanol, and the like; esters such as n-butyl acetate, n-hexyl acetate, pentyl propionate, and the like; ethers such as the monoethyl, monobutyl and monohexyl ethers of ethylene glycol, and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like; aromatic hydrocarbons such as xylene, or toluene, and the like; aliphatic or alicyclic hydrocarbons such as the various petroleum naphthas and cyclohexane; and mixture
- the film-forming composition can also be waterborne.
- the composition can contain an acid functional polymer that can be neutralized with amines and dissolved or dispersed in water.
- the diluent can optionally contain water-soluble organic cosolvents, for example alcohols with up to about eight carbon atoms such as methanol, ethanol, propanol, butanol, isobutanol, or mixtures thereof; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and the like.
- water-soluble organic cosolvents for example alcohols with up to about eight carbon atoms such as methanol, ethanol, propanol, butanol, isobutanol, or mixtures thereof; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and the like.
- diluents are typically used at a level of up to about 50 percent, preferably up to about 40 percent by weight, based on the total weight of the film-forming composition.
- the film-forming composition can also be used in particulate form, i.e., as a powder coating, in which the acrylic polymer and the oligomer or polymer containing the repeating ester groups are chosen such that they have a glass transition temperature (Tg) greater than 60°C. These materials can then be combined with an aldehyde condensate of glycouril, as previously mentioned, to form a powder film- forming composition.
- Tg glass transition temperature
- the coating composition is a thermosetting composition and typically contains catalysts to accelerate the curing reactions.
- the catalysts are acidic materials. Sulfonic acids, substituted sulfonic acids and amine neutralized sulfonic acids are preferred, for example, p-toluene sulfonic acid, dodecyl benzene sulfonic acid, dinonylnaphthalene disulfonic acid, and the like.
- the catalyst is usually present in an amount of from 0.50 to 5.0 percent, preferably from 0.5 to 1.0 percent, the percentages based on the total weight of resin solids in the coating composition.
- the coating composition can contain other optional ingredients, such as co-reactive resinous materials; plasticizers; anti-oxidants; UV light absorbers; surfactants; flow control agents; anti-settling agents; and the like. When present, these materials are generally used at a level up to 25 percent, preferably up to 10 percent by weight, the percentages based on the total weight of resin solids in the coating composition.
- the film-forming composition can be applied to any of the various substrates to which it adheres.
- suitable substrates include metals, wood, glass, cloth, plastic, foam, elastomeric substrates, and the like.
- the substrate is metal or plastic.
- the substrate could have been previously coated with a primer coating composition, or with a pigmented basecoat and the film-forming composition of the present invention applied as a clear coat over the pigmented base coat to form a color plus clear composite coating.
- compositions can be applied by conventional means including brushing, dipping, flow coating, spraying, and the like. Preferably, they are applied by spraying.
- spraying The usual spray techniques and equipment for air-spraying or electrostatic spraying can be used.
- pigmented base coat is first applied to a substrate at a uniform film thickness of from about 0.25 to about 1.5 mils.
- the base coat is then "flashed, " that is, it is left to stand at temperatures ranging from the ambient temperature to 80"C for about 10 seconds to 30 minutes, before another coating composition is applied to it.
- the clear coating composition of the present invention is applied over the coated substrate in one or more coats to a uniform film thickness from 0.5 to 5.0 mils.
- the substrate is then flashed again and finally baked until the film is cured, typically for about 20 minutes to about 40 minutes at from about 100°C to about 200°C to produce the coated article.
- the base coating compositions are those well known in the art as described, for example, in U.S. Patent No. 4,681,811, column 1, line 56 to column 4, line 2.
- a carbamate functional acrylic polymer was prepared from the following ingredients:
- DOWANOL PM 3 2.5 butyl stannoic acid 0.5 triphenylphosphite 0.3
- DOWANOL PM carbamate 4 (37% solution in DOWANOL PM) 219.1
- the first ingredient was charged to a suitable reactor under an N 2 blanket and heated to 155°C.
- the next two ingredients were mixed together and added to the reactor at a constant rate over 3.5 hours.
- Addition of a mixture of hydroxypropyl acrylate, butyl methacrylate, methyl styrene dimer, and EXXATE 600 was begun 15 minutes after the beginning of the first addition and added at a constant rate over 3 hours.
- a rinse of EXXATE 600 followed both additions.
- the reaction was held at temperature for 1 hour.
- a mixture of di- t-amyl peroxide and EXXATE 600 was then added to the reactor over a period of 0.5 hour , followed by a EXXATE 600 rinse. The reaction was held for an additional 3 hours.
- the reaction was then cooled to 140°C. While the reaction was cooling, triphenylphosphite was added to the reactor, followed by an EXXATE 600 rinse. Solvent was then distilled from the reactor under reduced pressure. DOWANOL PM and butyl stannoic acid were added to the reactor as a slurry, followed by triphenylphosphite and a DOWANOL PM rinse. The DOWANOL PM carbamate was added to the reactor over a period of 3 hours. During the addition, DOWANOL PM was distilled from the reactor under reduced pressure. Upon completion of the addition a DOWANOL PM rinse was added to the reactor. The reaction was continued until DOWANOL PM evolution stopped. The resin prior to dilution had a residual hydroxyl value of 26.5.
- the resin was diluted with a 1:1 mixture of ethyl 3-ethoxypropionate and DOWANOL PM. After dilution, the resin had a measured solids content of 66.5% and a Gardner-Holt viscosity of U- .
- the carbamate functional acrylic polymer had a number average molecular weight (Mn) of 1176 and a weight average molecular weight (Mw) of 2721 as determined by gel permeation chromatography using a polystyrene standard.
- a carbamate functional polyester polymer was prepared from the following ingredients: Ingredients Wei ⁇ ht in parts
- DOWANOL PM carbamate (37% solution in DOWANOL PM) 318.9 DOWANOL PM 10.0 DOWANOL PM 105.0
- the first ingredient was charged to a suitable reactor equipped with a glycol recovery column.
- Deionized H 2 0 was added to the reactor as a rinse for the first ingredient.
- Trimethylolpropane, butyl stannoic acid, and triphenylphosphite were then added to the reactor, followed by a deionized H 2 0 rinse.
- the reaction mixture was then heated to 77°C and sparged with nitrogen for 20 minutes.
- the reaction mixture was heated to 210°C and H 2 0 was removed from the reactor with the nitrogen sparge.
- the reaction was held to an acid value of 10.2 and the batch cooled to 140°C.
- the intermediate resin had a hydroxyl value of 156.6.
- DOWANOL PM and butyl stannoic acid were added to the reactor as a slurry, followed by addition of triphenylphosphite and a DOWANOL PM rinse.
- DOWANOL PM carbamate in DOWANOL PM solution was added to the reactor over a period of 4 hours. During the addition, DOWANOL PM was distilled from the reactor under reduced pressure. Upon completion of the addition a DOWANOL PM rinse was added to the reactor. The reaction was continued until DOWANOL PM evolution stopped. A sample of resin (90 parts) was removed from the reactor; the remaining resin was diluted with DOWANOL PM.
- the resin prior to dilution had a residual hydroxyl value of 19.4 and an acid value of 8.5. After dilution, the resin had a measured solids content of 71.2% and a Gardner-Holt viscosity of Z1+.
- the carbamate functional polyester polymer had an Mn of 720 and an Mw of 2220 as determined by gel permeation chromatography using a polystyrene standard.
- a solution of a hydroxyl functional polyester was prepared from the following ingredients: Ingredient weight in grams polyester 1 600.0 DOWANOL PM 150.0
- a hydroxyl terminated ester oligomer was prepared from the following ingredients:
- the first three ingredients were charged to a suitable reactor and heated to 115°C under a nitrogen blanket. Methylhexahydrophthalic anhydride was added to the reactor dropwise over a period of 2 hours and the reaction held at temperature until the anhydride was consumed as determined by IR spectroscopy. The reaction temperature was raised to 120°C and CARDURA E was added to the reactor dropwise over a period of 4 hours. The reaction was held at temperature to a acid value of 12.4 and an epoxy equivalent weight of 22,500. After dilution with DOWANOL PM, the final product had a measured solids content of 84.6% and a viscosity of Z4- on the Gardner- Holt viscosity scale. The hydroxyl terminated ester oligomer had an Mn of 1047 and an Mw of 1274 as determined by gel permeation chromatography using a polystyrene standard.
- EXAMPLE E A partially defunctionalized polyester was prepared from the following ingredients: Ingredient Weight in grams polyester used in Example C 381.3 dibutyl in oxide 0.5 isopropenyl acetate 130.0 DOWANOL PM 141.1
- the first two ingredients were charged to a suitable reactor equipped for fractional distillation and .heated to 130°C.
- Isopropenyl acetate was added dropwise to the polyester over a period of 4 hours.
- Acetone was removed from the reactor by distillation.
- the material before dilution had a measured OH value of 47.5.
- the reaction mixture had a final solids content of 75.4% and a viscosity of U- on the Gardner-Holt scale.
- the partially defunctionalized polyester had an Mn of 1258 and an Mw of 2987 as determined by gel permeation chromatography using a polystyrene standard.
- EXAMPLE F A hydroxyl terminated linear polyester was prepared from the following ingredients: Ingredient methylhexahydrophthalic anhydride 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl- 3-hydroxypropyl propionate butyl stannoic acid triphenylphosphite DOWANOL PM
- the first four ingredients were charged to a suitable reactor equipped with a nitrogen sparge and a glycol recovery column and heated to 210°C. As water was removed from the reaction, the acid value of the reaction mixture dropped to 9.4. The reaction mixture was cooled and diluted with DOWANOL PM. After dilution, the reaction mixture had a measured solids content of 79.0% and a viscosity of W- on the Gardner-Holt scale.
- the hydroxyl terminated linear polyester had an Mn of 939 and an Mw of 1626 as determined by gel permeation chromatography using a polystyrene standard.
- EXAMPLE G An acid functional polyester was prepared from the following ingredients: Ingr d ent Wei ⁇ ht in grams polyester used in Example C 424.65 butyl acetate 64.60 methylhexahydrophthalic anhydride 156.41
- DOWANOL PM 129.09 The first two ingredients were charged to a suitable reactor and heated to 115°C under a nitrogen blanket. Methylhexahydrophthalic anhydride was added dropwise to the reactor over a period of 2 hours, then held for an additional 4 hours until the anhydride was consumed as determined by IR spectroscopy. The material before dilution had a measured residual hydroxyl value of 8.4. After dilution with DOWANOL PM, the reaction mixture had a final solids content of 74.8%, a viscosity of U on the Gardner-Holt scale and an acid value of 65.2. The acid functional polyester had an Mn of 1572 and an Mw of 3103 as determined by gel permeation chromatography using a polystyrene standard.
- EXAMPLE H A carbamate functional polyester was prepared from the following ingredients: Ingredients Weight in grams trimethylolpropane 2680.0 methylhexahydrophthalic anhydride 3964.8
- the first five ingredients were charged to a suitable reactor equipped with a nitrogen sparge and a glycol recovery column and heated to 210°C. As water was removed from the reaction, the acid value of the reaction mixture dropped to 10. The intermediate resin was then cooled to 140°C. Butyl stannoic acid and triphenylphosphite were added to the reactor. The DOWANOL PM carbamate was added to the reactor over a period of 4 hours. During the addition, DOWANOL PM was distilled from the reactor under reduced pressure. The reaction was continued until DOWANOL PM evolution stopped. Prior to dilution, the material had a residual OH value of 71.9. The resin was diluted with n-propanol.
- the carbamate functional polyester had an Mn of 2159 and an Mw of 29,535 as determined by gel permeation chromatography using a polystyrene standard.
- a carbamate functional polyester was prepared from the following ingredients : Ingredients weight in grams trimethylolpropane 162 . 4 methylhexahydrophthalic anhydride 732 . 5 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl- 743 . 7 3-hydroxypropyl propionate butyl stannoic acid 2.4 triphenylphosphite 1.6 butyl stannoic acid 2.0 triphenylphosphite 2.0 DOWANOL PM carbamate (37% solution 933.4 in DOWANOL PM) DOWANOL PM 710.0
- the first five ingredients were charged to a suitable reactor equipped with a nitrogen sparge and a glycol recovery column and heated to 210°C. As water was removed from the reaction, the acid value of the reaction mixture dropped to 10.1. The intermediate resin was then cooled to 140°C. Butyl stannoic acid and triphenylphosphite were added to the reactor. DOWANOL PM carbamate in DOWANOL PM solution was added to the reactor over a period of 4 hours. During the addition, DOWANOL PM was distilled from the reactor under reduced pressure. The reaction was continued until DOWANOL PM evolution stopped. Before dilution, the material had a residual OH value of 26.0. The resin was diluted with DOWANOL PM.
- a OH terminal polyester urethane resin was prepared from the following ingredients: Ingredient Weight in grams polyester 1 312.8
- the hydroxyl terminal polyester urethane had an Mn of 1201 and an Mw of
- Example 1 shows the preparation of various clear film-forming compositions prepared with aminoplast curing agents, carbamate functional acrylic, and polyester materials. The coating compositions were evaluated in color-plus-clear applications.
- Example 1 shows the preparation of various clear film-forming compositions prepared with aminoplast curing agents, carbamate functional acrylic, and polyester materials. The coating compositions were evaluated in color-plus-clear applications.
- a clear film-forming composition was prepared by mixing together the following ingredients:
- Example 2 A clear film-forming composition was prepared by mixing together the following ingredients: Ingredient Solid weight in gra s Solution weight in grams n-amyl propionate 28.1 methyl n-amyl ketone 17.6
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 52.0 (80%) 78.1 carbamate containing polyester of Example B 13.0 (20%) 18.3
- Example 3 A clear film-forming composition was prepared by mixing together the following ingredients:
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 39.0 (60%) 58.6 carbamate containing polyester of Example B 26.0 (40%) 36.6
- Example 4 A clear film-forming composition was prepared by mixing together the following ingredients : Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 30.6 methyl n-amyl ketone 17.6
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 26.0 (40%) 39.0 carbamate containing polyester of Example B 39.0 (60%) 54.9
- Example 5 A clear film-forming composition was prepared by mixing together the following ingredients :
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 13.0 (20° 19.5 carbamate containing polyester of Example B 52.0 (80%) 73.2
- Example 6 A clear film-forming composition was prepared by mixing together the following ingredients: Ing edient Sol d weight in grams Solution weight in grams n-amyl propionate 33.0 methyl n-amyl ketone 17.6
- Example 7 A clear film-forming composition was prepared by mixing together the following ingredients :
- a clear film-forming composition was prepared by mixing together the following ingredients : Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 28.4 methyl n-amyl ketone 13.6
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 39.0 (60? 58.6 hydroxyl containing polyester of Example C 26.0 (40%) 32.5
- Example 9 A clear film-forming composition was prepared by mixing together the following ingredients :
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 26.0 (40%) 39.0 hydroxyl containing polyester of Example C 39.0 (60%) 48.8
- Example 10 A clear film-forming composition was prepared by mixing together the following ingredients: Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 30.0 methyl n-amyl ketone 10.0
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 13.0 (20%) 19.5 hydroxyl containing polyester of Example C 52.0 (80%) 65.0
- Example 12 A clear film- orming composition was prepared by mixing together the following ingredients : Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 32.2 methyl n-amyl ketone 10.0
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 32.5 (50%: 48.9 hydroxyl containing oligomer of Example D 32.5 (50? 38.4
- Example 13 A clear film-forming composition was prepared by mixing together the following ingredients :
- a clear film-forming composition was prepared by mixing together the following ingredients: Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 24.5 methyl n-amyl ketone 14.0
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 32.5 (50%) 48.9 hydroxyl containing polyester of Example F 32.5 (50%) 41.1
- Example 15 A clear film-forming composition was prepared by mixing together the following ingredients:
- a clear film-forming composition was prepared by mixing together the following ingredients: Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 39.2 methyl n-amyl ketone 27.5
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 32.5 (50%) 48.9 carbamate containing polyester of Example H 32.5 (50%) 41.4
- Example 17 A clear film-forming composition was prepared by mixing together the following ingredients :
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 32.5 (50%) 48.9 carbamate containing polyester of Example I 32.5 (50%) 44.2
- Example 18 A clear film-forming composition was prepared by mixing together the following ingredients: Ingredient Solid weight in grams Solution weight in grams n-amyl propionate 34.7 methyl n-amyl ketone 15.0
- CYMEL 327 1 35.0 38.9 carbamate containing acrylic of Example A 39.0 (60%) 58.6 hydroxyl containing polyester of Example C 26.0 (40%) 32.5
- Example 19 A clear film-forming composition was prepared by mixing together the following ingredients:
- a partially alkylated aminoplast resin available from Cytec Industries which contains approximately 66% methoxy, • 3% imino, and 31% methylol functionality by weight.
- Example 20 A clear film-forming composition was prepared by mixing together the following ingredients:
- Example 21 A clear film-forming composition was prepared by mixing together the following ingredients : Ingredient Solid weight in ms Solution weight in grams n-amyl propionate 31.1 methyl n-amyl ketone 10.0
- CYMEL 1130 35.0 35.0 carbamate containing acrylic of Example A 32.5 (50%) 48.9 hydroxyl containing poly(ester urethane) of Example J 32.5 (50%) 39.5
- the film-forming compositions of Examples 1-21 were applied to pigmented basecoats to form color-plus-clear composite coatings over electrocoated steel substrates.
- the basecoats used for examples 1-21 are commercially available from PPG Industries, Inc. and are identified as DCT-6373 (black in color) and DCT-6720 (silver metallic) .
- the electrocoat used on the steel is commercially available from PPG Industries, Inc. and is identified as ED-5000.
- the basecoat was spray applied in two coats to electrocoated steel panels at a temperature of about 75°F (24°C) .
- a ninety second flash time was allowed between the two basecoat applications.
- a flash time of 5 to 10 minutes was allowed at 75°F (24°C) before the application of the clear coating composition.
- the clear coating compositions of Examples 1-21 were each applied to a basecoated panel in two coats with a ninety second flash at 75°F (24°C) allowed between coats.
- the composite coating was allowed to air flash at 75°F (24°C) for 10 to 15 minutes before baking at 285°F (141°C) to cure both the basecoat and the clearcoat.
- the panels were baked in a horizontal position.
- One black and one silver colored panel for each clearcoat example was baked for 25 minutes and used to test appearance, acid etch resistance, and humidity resistance.
- a second black colored panel for each clearcoat example was prepared using the identical application procedure described above, however these panels were baked for one hour at 285°F (141°C) , to cure both the basecoat and the clearcoat, at which point each panel was allowed to cool, and then the same clearcoat example was reapplied directly to the surface of the first fully-cured clearcoat without sanding or applying an additional layer of basecoat. The panels were then baked for 25 minutes at 285°F (141°C) to cure the additional layer of clearcoat.
- polyester oligomer defunctionalized polyester polyester made with all diol acid functional polyester polyester made with triol/diol mole ratio of 3.3/1.
- high molecular weight polyeste partially alkylated aminoplast made with all diol acid functional polyester polyester made with triol/diol mole ratio of 3.3/1.
- a solution of 350 parts deionized water and 12 parts sulfurous acid was prepared.
- the acid solution was sprayed onto the panels using a polyethylene spray bottle, giving a distribution of drop sizes up to one quarter inch. Approximately 1.5 grams of solution was applied per 2x4 inch panel.
- the panels were then placed in an oven at 120°F (49°C) for twenty minutes. The panels were removed from the oven and the spray/bake procedure was repeated two more times to give a total of 60 minutes at 120°F (49°C) .
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US494905 | 1995-06-26 | ||
US08/494,905 US5593785A (en) | 1995-06-26 | 1995-06-26 | Coating compositions containing acrylic polymers with pendant carbamate groups exhibiting improved intercoat adhesion |
PCT/US1996/010417 WO1997001608A1 (fr) | 1995-06-26 | 1996-06-14 | Compositions pour enduits contenant des polymeres acryliques a groupes carbamate pendants |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0835293A1 true EP0835293A1 (fr) | 1998-04-15 |
EP0835293B1 EP0835293B1 (fr) | 1999-10-20 |
Family
ID=23966446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96919448A Expired - Lifetime EP0835293B1 (fr) | 1995-06-26 | 1996-06-14 | Compositions pour enduits contenant des polymeres acryliques a groupes carbamate pendants |
Country Status (10)
Country | Link |
---|---|
US (1) | US5593785A (fr) |
EP (1) | EP0835293B1 (fr) |
JP (1) | JP3064424B2 (fr) |
AU (1) | AU6178896A (fr) |
BR (1) | BR9609220A (fr) |
CA (1) | CA2219497C (fr) |
DE (1) | DE69604804T2 (fr) |
ES (1) | ES2140862T3 (fr) |
MX (1) | MX9710185A (fr) |
WO (1) | WO1997001608A1 (fr) |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW242644B (fr) * | 1992-10-30 | 1995-03-11 | Ppg Industries Inc | |
JP2672031B2 (ja) * | 1992-10-30 | 1997-11-05 | ピーピージー インダストリーズ,インコーポレイテッド | 耐酸エッチング性を有する塗膜を与えるアミノプラスト硬化可能な塗膜形成組成物 |
US5709950A (en) * | 1994-04-29 | 1998-01-20 | Ppg Industries, Inc. | Color-plus-clear composite coatings that contain polymers having carbamate functionality |
US5976701A (en) * | 1994-04-29 | 1999-11-02 | Ppg Industries Ohio, Inc. | Flexible aminoplast-curable film-forming compositions and composite coating |
US5759694A (en) * | 1996-09-04 | 1998-06-02 | Ppg Industries, Inc. | Carbamate functional polymers and oligomers and coating compositions containing same |
US5959040A (en) * | 1996-09-04 | 1999-09-28 | Ppg Industries Ohio, Inc. | Film-forming composition suitable for use as a monocoat |
US5922475A (en) * | 1997-04-29 | 1999-07-13 | Ppg Industries Ohio, Inc. | Color-plus-clear composite coating compositions containing alkylolated or etherified carbanate functional polymers |
CA2239893A1 (fr) * | 1997-06-30 | 1998-12-30 | Gregory G. Menovcik | Compositions de revetement primaires renfermant des polymdres novolaques ou acryliques avec fonction carbamate |
US5859154A (en) * | 1997-09-26 | 1999-01-12 | Ppg Industries, Inc. | Resinous composition of phosphatized polyester polymers and coating compositions for improved adhesion |
WO1999024512A1 (fr) | 1997-11-06 | 1999-05-20 | The Edgington Company | Composition pour revetement |
US6071568A (en) * | 1998-05-01 | 2000-06-06 | Basf Corporation | Method for improving appearance in composite color-plus-clear coatings and compositions for use therein |
US6045872A (en) * | 1998-05-01 | 2000-04-04 | Basf Corporation | Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein |
ATE263223T1 (de) * | 1999-09-30 | 2004-04-15 | Basf Corp | Carbamatfunktionelle harze mit verbesserter adhäsion, verfahren zu deren herstellung und verfahren zur verbesserung der zwischenhaftung |
US6437036B1 (en) * | 1999-11-17 | 2002-08-20 | Basf Corporation | Waterborne primer with improved chip resistance |
US6824849B2 (en) | 2000-08-07 | 2004-11-30 | 3M Innovative Properties Company | Laser-cuttable multi-layer sheet material |
US6657007B2 (en) | 2000-09-29 | 2003-12-02 | Basf Corporation | Clearcoat composition with improved adhesion |
KR100390647B1 (ko) * | 2001-02-12 | 2003-07-04 | 썬스타 산업봉제기계 주식회사 | 멀티헤드 재봉기용 재봉위치 표시장치 |
US6555231B2 (en) | 2001-07-03 | 2003-04-29 | Basf Corporation | Waterborne coating composition and a paint system thereof having improved chip resistance |
US20030134970A1 (en) * | 2002-01-17 | 2003-07-17 | Basf Corporation | Basecoat coating composition having low volatile organic content and composite coating prepared therefrom |
US6716953B2 (en) * | 2002-05-16 | 2004-04-06 | Ppg Industries Ohio, Inc. | Etherified carbamate crosslinking agents and their use in curable compositions, particularly film-forming compositions |
US7342071B2 (en) * | 2002-10-31 | 2008-03-11 | Basf Corporation | Clearcoat paint composition |
US20040087728A1 (en) * | 2002-10-31 | 2004-05-06 | Donald Campbell | Carbamate functional addition polymers and a method for their preparation |
US7232863B2 (en) | 2002-10-31 | 2007-06-19 | Basf Corporation | Functional addition polymers and a method for their preparation |
US7045588B2 (en) * | 2004-02-12 | 2006-05-16 | Basf Corporation | Polyester resin composition for use in a coating composition and method of preparing the same |
US8318849B2 (en) * | 2006-04-21 | 2012-11-27 | Basf Coatings Gmbh | High solids nonaqueous dispersion clearcoats |
KR100853170B1 (ko) * | 2006-04-29 | 2008-08-20 | 주식회사 잉크테크 | 고광택 알루미늄휠의 제조방법 |
US7807743B2 (en) * | 2006-09-22 | 2010-10-05 | Basf Corporation | Coating composition and film system therefrom |
US20080249226A1 (en) * | 2007-04-09 | 2008-10-09 | Nan Ya Plastics Corporation | Waterborne coating compositions for optical-use polyester film |
US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
US20110021694A1 (en) * | 2009-07-23 | 2011-01-27 | E.I. Du Pont De Nemours And Company | Polyesterurethane for coating compositions |
MX344924B (es) | 2010-03-04 | 2017-01-11 | Avery Dennison Corp | Película distinta de pvc y laminado de película distinta de pvc. |
US10196484B2 (en) | 2013-09-17 | 2019-02-05 | Dow Global Technologies Llc | Method for producing polycarbamate, a polycarbamate produced thereby and a coating containing the polycarbamate |
EP3090013B1 (fr) | 2013-12-30 | 2020-09-09 | Avery Dennison Corporation | Film protecteur en polyuréthane |
US20150210795A1 (en) * | 2014-01-30 | 2015-07-30 | Basf Coatings Gmbh | Amphiphilic carbamate-functional copolymers and coatings containing them |
JP5935949B2 (ja) * | 2014-02-28 | 2016-06-15 | 新日鐵住金株式会社 | プレコート金属板、プレコート金属板の製造方法 |
US12134705B2 (en) | 2018-10-11 | 2024-11-05 | Eastman Chemical Company | Scratch resistant thermosetting coating compositions |
CN116323554A (zh) | 2021-01-05 | 2023-06-23 | 巴斯夫涂料有限公司 | 使用氨基甲酸叔丁酯和锡催化剂制备氨基甲酸酯官能物质的方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4543276A (en) * | 1983-03-28 | 1985-09-24 | American Cyanamid Company | Thermosetting polyurethane compositions |
US5356669A (en) * | 1992-10-23 | 1994-10-18 | Basf Corporation | Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat |
ZA937635B (en) * | 1992-10-23 | 1994-05-05 | Basf Corp | Curable carbamate-functional polymer composition |
US6103816A (en) * | 1992-10-30 | 2000-08-15 | Ppg Industries Ohio, Inc. | Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching |
US5744550A (en) * | 1994-11-03 | 1998-04-28 | Basf Corporation | Curable coating compositions containing carbamate additives |
US5512639A (en) * | 1993-07-28 | 1996-04-30 | Basf Corporation | Curable compositions containing carbamate-modified polyisocyanates |
US5373069A (en) * | 1993-07-28 | 1994-12-13 | Basf Corporation | Curable carbamate-functional polymers |
US5412049A (en) * | 1994-03-31 | 1995-05-02 | Union Carbide Chemicals & Plastics Technology Corporation | Polymer compositions containing hydroxyl functional (meth)acrylates and hydroxyalkyl carbamate (meth)acrylates and mixtures thereof |
-
1995
- 1995-06-26 US US08/494,905 patent/US5593785A/en not_active Expired - Lifetime
-
1996
- 1996-06-14 CA CA002219497A patent/CA2219497C/fr not_active Expired - Fee Related
- 1996-06-14 DE DE69604804T patent/DE69604804T2/de not_active Expired - Lifetime
- 1996-06-14 BR BR9609220A patent/BR9609220A/pt not_active IP Right Cessation
- 1996-06-14 JP JP9504448A patent/JP3064424B2/ja not_active Expired - Fee Related
- 1996-06-14 ES ES96919448T patent/ES2140862T3/es not_active Expired - Lifetime
- 1996-06-14 EP EP96919448A patent/EP0835293B1/fr not_active Expired - Lifetime
- 1996-06-14 WO PCT/US1996/010417 patent/WO1997001608A1/fr active IP Right Grant
- 1996-06-14 AU AU61788/96A patent/AU6178896A/en not_active Abandoned
- 1996-06-14 MX MX9710185A patent/MX9710185A/es unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9701608A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE69604804D1 (de) | 1999-11-25 |
JPH10510320A (ja) | 1998-10-06 |
BR9609220A (pt) | 1999-06-08 |
WO1997001608A1 (fr) | 1997-01-16 |
ES2140862T3 (es) | 2000-03-01 |
DE69604804T2 (de) | 2000-04-27 |
CA2219497A1 (fr) | 1997-01-16 |
EP0835293B1 (fr) | 1999-10-20 |
US5593785A (en) | 1997-01-14 |
CA2219497C (fr) | 2002-02-05 |
MX9710185A (es) | 1998-03-31 |
JP3064424B2 (ja) | 2000-07-12 |
AU6178896A (en) | 1997-01-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5593785A (en) | Coating compositions containing acrylic polymers with pendant carbamate groups exhibiting improved intercoat adhesion | |
US5593733A (en) | Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers | |
EP0666875B1 (fr) | Procede de preparation de revetements composites a couches coloree et transparente resistant a l'attaque de l'acide | |
US6228974B1 (en) | Aminoplast curable film-forming compositions providing films having resistance to acid etching | |
US6235858B1 (en) | Aminoplast curable film-forming compositions providing films having resistance to acid etching | |
JP2009511253A (ja) | 車体へのプライマ焼付無しでの多層コーティングの形成方法 | |
KR19990008255A (ko) | 내스크래치성 코팅 조성물 | |
EP1453864B1 (fr) | Procede d'obtention de compositions de revetement a cov reduit | |
US5759694A (en) | Carbamate functional polymers and oligomers and coating compositions containing same | |
US5959040A (en) | Film-forming composition suitable for use as a monocoat |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19980116 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT PT SE |
|
17Q | First examination report despatched |
Effective date: 19980807 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: PPG INDUSTRIES OHIO, INC. |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT PT SE |
|
REF | Corresponds to: |
Ref document number: 69604804 Country of ref document: DE Date of ref document: 19991125 |
|
ITF | It: translation for a ep patent filed | ||
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 19991109 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2140862 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20080730 Year of fee payment: 13 |
|
BERE | Be: lapsed |
Owner name: *PPG INDUSTRIES OHIO INC. Effective date: 20090630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090630 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20100520 Year of fee payment: 15 Ref country code: FR Payment date: 20100630 Year of fee payment: 15 Ref country code: ES Payment date: 20100628 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20100629 Year of fee payment: 15 Ref country code: IT Payment date: 20100629 Year of fee payment: 15 Ref country code: GB Payment date: 20100625 Year of fee payment: 15 Ref country code: DE Payment date: 20100629 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20111214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111214 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20110614 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110614 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20120229 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69604804 Country of ref document: DE Effective date: 20120103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110630 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110614 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110615 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20130531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110615 |